Scaled Synthesis of Polyamine-Modified Cellulose Nanocrystals from Bulk Cotton and Their Use for Capturing Volatile Organic Compounds.

We have previously demonstrated that cellulose nanocrystals modified with poly(ethylenimine) (PEI-f-CNC) are capable of capturing volatile organic compounds (VOCs) associated with malodors. In this manuscript, we describe our efforts to develop a scalable synthesis of these materials from bulk cotton. This work culminated in a reliable protocol for the synthesis of unmodified cellulose nanocrystals (CNCs) from bulk cotton on a 0.5 kg scale. Additionally, we developed a protocol for the modification of the CNCs by means of sequential 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) oxidation and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) coupling to modify their surface with poly(ethylenimine) on a 100 g scale. Subsequently, we evaluated the performance of the PEI-f-CNC materials that were prepared in a series of VOC capture experiments. First, we demonstrated their efficacy in capturing volatile fatty acids emitted at a rendering plant when formulated as packed-bed filter cartridges. Secondly, we evaluated the potential to use aqueous PEI-f-CNC suspensions as a spray-based delivery method for VOC remediation. In both cases, the PEI-f-CNC formulations reduced detectable malodor VOCs by greater than 90%. The facile scaled synthesis of these materials and their excellent performance at VOC remediation suggest that they may emerge as a useful strategy for the remediation of VOCs associated with odor.

Cellulose particles capture aldehyde VOC pollutants.

Aldehydes are commonly encountered Volatile Organic Compounds (VOCs) released to the atmosphere from a variety of anthropogenic sources. Based on the increasing interest in developing sustainable and environmentally friendly materials for the decontamination of VOCs, cellulose particles have emerged as one possible candidate, but there is a lack of understanding of the physicochemical properties affecting the adsorption of VOCs, and the effect of the extraction source on these intrinsic features. The present study was focused on the evaluation of unmodified cellulose particles extracted from biodiverse sources in Ecuador as potential VOC decontaminants. Modifications of the natural fibers with polyethylenimine (PEI) coating were performed to enhance the adsorption effectiveness. Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) measurements, and scanning electron microscopy (SEM) methods were used to characterize the physicochemical properties of the isolates. Gas chromatography assays demonstrated that unmodified cellulose can adsorb an aldehyde VOC, hexanal, reaching up to a 56.42 ± 7.30% reduction. Electrostatic coating of the cellulose particles with small quantities of PEI enhanced the VOC remediation capacities (i.e. 98.12 ± 1.18%). Results demonstrated that the biodiverse plant source of the cellulose isolate can affect the gas capturing properties, and that these particles can be an environmentally friendly solution for effective adsorption of VOC pollutants.

Degradation of pesticides using amine-functionalized cellulose nanocrystals.

A series of amine-functionalized cellulose nanocrystal materials were successfully synthesized, characterized, and evaluated for the remediation of pesticide contaminants from organic and aqueous media. Their ability to degrade malathion in organic systems has been examined, resulting in up to 100% degradation of the compound into detectable lower molecular weight by-products. A poly(ethylenimine) cellulose nanocrystal (CNC-PEI) material was also capable of degrading aqueous solutions of malathion, deltamethrin, and permethrin with 100%, 95%, and 78% degradation, respectively. Thus, these materials can potentially serve as a new and viable remediation technique based on their ability to effectively degrade various pesticides. The reusability of the CNC-PEI was also explored. The CNC-PEI material maintained its ability to degrade malathion throughout two wash and re-use cycles.

Strategies for High Grafting Efficiency of Functional Ligands to Lipid Nanoemulsions for RGD-Mediated Targeting of Tumor Cells In Vitro.

Lipid nanoemulsions (LNEs) are promising nanocarriers for delivering high payloads of lipophilic molecules. Nonetheless, the dynamic nature at their aqueous interfaces results in poor surface chemistry and thus ligand functionalization can be challenging. Herein, two independent strategies, postconjugation and preconjugation, were explored to prepare LNEs grafted covalently with model ligands, fluorescein dye and RGD peptide, respectively. Fluorescein was successfully conjugated with high grafting efficiency to an amine-functionalized lipid nanoemulsion (NH2-LNE) as determined by spectrophotometric analysis. First, we formulated NH2-LNEs by a low-energy spontaneous emulsification technique in the presence of oleylamine (OA) within the oily core of the nanodroplets, thus creating primary amine-reactive sites at the oil/water interface. These amines were used to incorporate fluorescein, yielding fluorescent LNEs with grafting efficiencies of 33, 69, and 69% at NH2-LNEs with [OA]oil = 0.18, 0.34, and 0.49 M, respectively. We also developed RGD-labeled LNEs (RGD-LNEs) and evaluated the nanomaterial with model cell lines that overexpress αVß3 integrins on their surfaces. To this end, we initially synthesized an RGD-Oleate fatty acid-peptide conjugate by solid-phase synthesis. The lipophilic segment of this conjugate readily embedded into the oily core of the LNE, and the hydrophilic head (RGD moiety) was oriented toward the LNE interface. In vitro cytotoxicity and cellular uptake studies were undertaken on different cancer cell lines including HaCaT human umbilical vein endothelial cells (HUVECs), MCF-7, and U-87 MG and compared to uptake experiments with RAW 264.7 macrophages. Confocal imaging and flow cytometry showed that RGD-LNEs were preferentially taken up by all of the tumor cell lines but showed very slight accumulation in RAW macrophages. Unmodified LNE controls did not show any appreciable cellular uptake. This work provides a simple and reliable methodology for the incorporation of multiple ligands on a single surface to facilitate active tumor targeting with LNE-based drug/imaging carriers for theranostic applications.

Periodic mesoporous organosilica nanomaterials for rapid capture of VOCs.

Periodic mesoporous organosilica nanoparticles (PMO SiNPs) were developed for the targeted capture of specific volatile organic compounds (VOCs). The removal kinetics for adsorbing VOCs were fast and the maximum removal could be achieved within less than 30 min. PMO SiNPs removed >99% of VOCs at a low sorbent dose (i.e. >0.5 mL analyte per g PMO SiNPs). They also showed good recyclability and maintained reasonable removal efficiencies after five cycles (i.e. 77% and 65% for hexanal and butyric acid vapors, respectively).

Poly(amine) modified kaolinite clay for VOC capture.

Polyethylenimine (PEI) functionalized kaolinite clay was successfully prepared, characterized, and assessed for the remediation of volatile organic compounds (VOCs) comprising the aldehyde, carboxylic acid, and disulfide functional group classes. A gas chromatographic vapor capture assay evaluated the capability of unmodified and modified clay material to capture representative aldehyde, carboxylic acid, and disulfide VOCs in a laboratory setting. Unmodified kaolinite (Kao) clay was moderately or poorly effective at remediating these VOCs, while the poly(amine) functionalized Kao was capable of capturing VOCs in the vapor phase with reductions up to 100%. Sample cartridge tubes were packed with PEI-functionalized clay in order to assess their ability to reduce the detectable volatile fatty acid load at an open-air rendering plant in a relevant field test for applying these materials in a packed-bed scrubber application. The PEI-Kao packed cartridges were capable of significantly reducing the detectable concentration of volatile fatty acid effluent from the rendering operation. These volatile fatty acids are major contributors to nuisance odors associated with rendering.

Evaluation of substituted ebselen derivatives as potential trypanocidal agents.

Human African trypanosomiasis is a disease of sub-Saharan Africa, where millions are at risk for the illness. The disease, commonly referred to as African sleeping sickness, is caused by an infection by the eukaryotic pathogen, Trypanosoma brucei. Previously, a target-based high throughput screen revealed ebselen (EbSe), and its sulfur analog, EbS, to be potent in vitro inhibitors of the T. brucei hexokinase 1 (TbHK1). These molecules also exhibited potent trypanocidal activity in vivo. In this manuscript, we synthesized a series of sixteen EbSe and EbS derivatives bearing electron-withdrawing carboxylic acid and methyl ester functional groups, and evaluated the influence of these substituents on the biological efficacy of the parent scaffold. With the exception of one methyl ester derivative, these modifications ablated or blunted the potent TbHK1 inhibition of the parent scaffold. Nonetheless, a few of the methyl ester derivatives still exhibited trypanocidal effects with single-digit micromolar or high nanomolar EC50 values.

Relative Rate Profiles of Functionalized Iodoarene Catalysts for Iodine(III) Oxidations.

A series of rate studies were conducted to evaluate the steric and electronic properties that govern the reactivity of iodoarene amide catalysts in the α-oxytosylation of propiophenone. A meta-substituted benzamide catalyst emerged as the most reactive. This catalyst was employed in the α-oxytosylation of a series of substituted propiophenones, returning the α-tosyloxy ketone products in excellent isolated yield.